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Synthetic, spectroscopic, and structural Studies on Lanthanide Complexes of Diphosphazane Dioxide Ligands
Author(s) -
Aparna Kasani,
Krishnamurthy Setharampattu S.,
Nethaji Munirathinam
Publication year - 1995
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.19956211114
Subject(s) - lanthanide , chemistry , crystallography , denticity , triclinic crystal system , ligand (biochemistry) , crystal structure , praseodymium , monoclinic crystal system , square antiprism , stereochemistry , inorganic chemistry , ion , biochemistry , receptor , organic chemistry
Abstract Lanthanide nitrate complexes of diphosphazane dioxides Ph 2 P(O)N(Pr i )P(O)Ph 2 ( 1 ) and (PhO) 2 P(O)N(Me)P(O)(OPh) 2 ( 2 ) have been synthesised and studied by conductometry, IR, multinuclear NMR spectroscopic methods and X‐ray diffraction. Ligand 2 is accessible by two different methods, viz. , by direct oxidation of the phosp(III)azane ligand or by starting from phosph(V)azane chloro precursor. The structure of 2 is confirmed by X‐ray diffraction. Crystallographic data for 2 : Triclinic, Space group P 1 , a = 10.078(1), b = 10.575(3), c = 12.364(4) Å, α = 75.70(2)°, α = 75.56(1)°, γ = 77.68(1)°, Z = 2, V = 1 220 Å 3 ; structure refined to R F = 0.0459 on 3 495 data with F > 3σ(F). The diphosphazane dioxide ligand exhibits trans geometry in the solid state. The structure of a lanthanide complex, [Pr(NO 3 ) 3 ( 2 ) 2 ] ( 14 ) is also determined by X‐ray diffraction. Crystallographic data for 14 : Trigonal, Space group P3 2 , a = b = 15.710(2), c = 40.067(2) Å, Z = 6, V = 8 564 Å 3 ; structure refined to R F = 0.0430 on 8 077 data with F > 5σ(F). The two diphosphazane dioxide ligands and the nitrate groups are coordinated to praseodymium in a bidentate chelate fashion. The geometry around the ten coordinated metal is distorted bicapped square antiprism.

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